Luminescent Ln-Ionic Liquids beyond Europium.

Searching in the Web of Knowledge for "ionic liquids" AND "luminescence" AND "lanthanide", around 260 entries can be found, of which a considerable number refer solely or primarily to europium (90%, ~234). Europium has been deemed the best lanthanide for luminescent applications, mainly due to its efficiency in sensitization, longest decay times, and the ability to use its luminescence spectra to probe the coordination geometry around the metal. The remaining lanthanides can also be of crucial importance due to their different colors, sensitivity, and capability as probes. In this manuscript, we intend to shed some light on the existing published work on the remaining lanthanides. In some cases, they appear in papers with europium, but frequently in a subordinate position, and in fewer cases then the main protagonist of the study. All of them will be assessed and presented in a concise manner; they will be divided into two main categories: lanthanide compounds dissolved in ionic liquids, and lanthanide-based ionic liquids. Finally, some analysis of future trends is carried out highlighting some future promising fields, such as ionogels.

Synthesis, structure and bonding of actinide disulphide dications in the gas phase.

Actinide disulphide dications, AnS22+, were produced in the gas phase for An = Th and Np by reaction of An2+ cations with the sulfur-atom donor COS, in a sequential abstraction process of two sulfur atoms, as examined by FTICR mass spectrometry. For An = Pu and Am, An2+ ions were unreactive with COS and did not yield any sulphide species. High level multiconfigurational (CASPT2) calculations were performed to assess the structures and bonding of the new AnS22+ species obtained for An = Th, Np, as well as for An = Pu to examine trends along the An series, and for An = U to compare with a previous experimental study and DFT computational scrutiny of US22+. The CASPT2 results showed that, like in the case of uranium, the new AnS22+ ions have ground states with triangular geometries, corresponding to the presence of a persulphide in the case of thorium that formally leads to a stable ThIVS22+ species, while a supersulphide appears to be present in the case of U, Np and Pu, formally leading to a AnIIIS22+ species. The computations also revealed that linear thioactinyl structures are higher in energy, with a difference that increases fourfold upon moving from U to Pu, apparently indicating that it will be even more pronounced for Am.

Magnetic properties of the layered lanthanide hydroxide series Y(x)Dy(8-x)(OH)20Cl4·6H2O: from single ion magnets to 2D and 3D interaction effects.

The magnetic properties of layered dysprosium hydroxides, both diluted in the diamagnetic yttrium analogous matrix (LYH:0.04Dy), and intercalated with 2,6-naphthalene dicarboxylate anions (LDyH-2,6-NDC), were studied and compared with the recently reported undiluted compound (LDyH = Dy8(OH)20Cl4·6H2O). The Y diluted compound reveals a single-molecule magnet (SMM) behavior of single Dy ions, with two distinct slow relaxation processes of the magnetization at low temperatures associated with the two main types of Dy sites, 8- and 9-fold coordinated. Only one relaxation process is observed in both undiluted LDyH and intercalated compounds as a consequence of dominant ferromagnetic Dy-Dy interactions, both intra- and interlayer. Semiempirical calculations using a radial effect charge (REC) model for the crystal field splitting of the Dy levels are used to explain data in terms of contributions from the different Dy sites. The dominant ferromagnetic interactions are explained in terms of orientations of easy magnetization axes obtained by REC calculations together with the sign of the superexchange expected from the Dy-O-Dy angles.

Synthesis and properties of uranium sulfide cations. An evaluation of the stability of thiouranyl, {S═U═S}2+.

Atomic uranium cations, U(+) and U(2+), reacted with the facile sulfur-atom donor OCS to produce several monopositive and dipositive uranium sulfide species containing up to four sulfur atoms. Sequential abstraction of two sulfur atoms by U(2+) resulted in US2(2+); density functional theory computations indicate that the ground-state structure for this species is side-on η(2)-S2 triangular US2(2+), with the linear thiouranyl isomer, {S═U(VI)═S}(2+), some 171 kJ mol(-1) higher in energy. The result that the linear thiouranyl structure is a local minimum at a moderate energy suggests that it should be feasible to stabilize this moiety in molecular compounds.

Europium(III) tetrakis(ß-diketonate) complex as an ionic liquid: a calorimetric and spectroscopic study.

An intrinsic photoluminescent ionic liquid based on europium(III) tetrakis(ß-diketonate) complex with a tetraalkylphosphonium as counterion was synthesized. Calorimetric measurements showed a melting point at 63 °C, which allows the ionic liquid classification. When cooling the material from the liquid state, metastable supercooled ionic liquid is obtained, as seen from NMR spectroscopy as well. Eu(III) photoluminescence is clearly observed while the absorption spectra of the ligand is dominant, showing the antenna effect. This was confirmed with submicrosecond time scale luminescence spectroscopy, where a rise of Eu(III) emission is observed with the correspondent decay of the ligand excited state. Temperature effects in the photoluminescence are also shown, being prominent above the melting point where the intensity decreases with Arrhenius behavior. Eu(III) luminescence decays also show features characteristic of energy migration between homologue Eu(III) species. Solvent effects were also studied by NMR and Luminescence spectroscopies, highlighting that the nucleophilicity of organic solvents such as n-alcohols leads to a coordination with Eu(III), which ultimately compromises the stability of the complex.

Thorium and uranium carbide cluster cations in the gas phase: similarities and differences between thorium and uranium.

Laser ionization of AnC4 alloys (An = Th, U) yielded gas-phase molecular thorium and uranium carbide cluster cations of composition An(m)C(n)(+), with m = 1, n = 2-14, and m = 2, n = 3-18, as detected by Fourier transform ion-cyclotron-resonance mass spectrometry. In the case of thorium, Th(m)C(n)(+) cluster ions with m = 3-13 and n = 5-30 were also produced, with an intriguing high intensity of Th13C(n)(+) cations. The AnC13(+) ions also exhibited an unexpectedly high abundance, in contrast to the gradual decrease in the intensity of other AnC(n)(+) ions with increasing values of n. High abundances of AnC2(+) and AnC4(+) ions are consistent with enhanced stability due to strong metal-C2 bonds. Among the most abundant bimetallic ions was Th2C3(+) for thorium; in contrast, U2C4(+) was the most intense bimetallic for uranium, with essentially no U2C3(+) appearing. Density functional theory computations were performed to illuminate this distinction between thorium and uranium. The computational results revealed structural and energetic disparities for the An2C3(+) and An2C4(+) cluster ions, which elucidate the observed differing abundances of the bimetallic carbide ions. Particularly noteworthy is that the Th atoms are essentially equivalent in Th2C3(+), whereas there is a large asymmetry between the U atoms in U2C3(+).

Chemistry and catalytic activity of molybdenum(VI)-pyrazolylpyridine complexes in olefin epoxidation. Crystal structures of monomeric dioxo, dioxo-µ-oxo, and oxodiperoxo derivatives.

The dioxomolybdenum(VI) complexes [MoO2Cl2(PzPy)] (1) and [MoO2(OSiPh3)2(PzPy)] (5) (PzPy = 2-[3(5)-pyrazolyl]pyridine) were synthesized and characterized by vibrational spectroscopy, with assignments being supported by DFT calculations. Complex 5 was additionally characterized by single crystal X-ray diffraction. Recrystallization of 1 under different conditions originated crystal structures containing either the mononuclear [MoO2Cl2(PzPy)] complex co-crystallized with 2-[3(5)-pyrazolyl]pyridinium chloride, binuclear [Mo2O4(µ2-O)Cl2(PzPy)2] complexes, or the oxodiperoxomolybdenum(VI) complex [MoO(O2)2Cl(PzPyH)], in which a 2-[3(5)-pyrazolyl]pyridinium cation weakly interacts with the Mo(VI) center via a pyrazolyl N-atom. The crystal packing in the different structures is mediated by a variety of supramolecular interactions: hydrogen bonding involving the pyridinium and/or pyrazolyl N-H groups, weak CH · · · O and CH · · · π contacts, and strong π-π stacking. Complexes 1 and 5 are moderately active catalysts for the epoxidation of cis-cyclooctene at 55 °C using tert-butylhydroperoxide as oxidant, giving 1,2-epoxycyclooctane as the only reaction product. Insoluble materials were recovered at the end of the first catalytic runs and characterized by IR spectroscopy, elemental analysis, scanning electron microscopy (SEM)-energy dispersive spectroscopy (EDS), and powder X-ray diffraction. For complex 5 the loss of the triphenylsiloxy ligands during the catalytic run resulted in the formation of a tetranuclear complex, [Mo4O8(µ2-O)4(PzPy)4]. The recovered solids could be used as efficient heterogeneous catalysts for the epoxidation of cyclooctene, showing no loss of catalytic performance between successive catalytic runs.

Actinide sulfides in the gas phase: experimental and theoretical studies of the thermochemistry of AnS (An = Ac, Th, Pa, U, Np, Pu, Am and Cm).

The gas-phase thermochemistry of actinide monosulfides, AnS, was investigated experimentally and theoretically. Fourier transform ion cyclotron resonance mass spectrometry was employed to study the reactivity of An(+) and AnO(+) (An = Th, Pa, U, Np, Pu, Am and Cm) with CS(2) and COS, as well as the reactivity of the produced AnS(+) with oxidants (COS, CO(2), CH(2)O and NO). From these experiments, An(+)-S bond dissociation energies could be bracketed. Density functional theory studies of the energetics of neutral and monocationic AnS (An = Ac, Th, Pa, U, Np, Pu, Am and Cm) provided values for bond dissociation energies and ionization energies; the computed energetics of neutral and monocationic AnO were also obtained for comparison. The theoretical data, together with comparisons with known An(+)-O bond dissociation energies and M(+)-S and M(+)-O dissociation energies for the early transition metals, allowed for the refining of the An(+)-S bond dissociation energy ranges obtained from experiment. Examination of the reactivity of AnS(+) with dienes, coupled to comparisons with reactivities of the AnO(+) analogues, systematic considerations and the theoretical results, allowed for the estimation of the ionization energies of the AnS; the bond dissociation energies of neutral AnS were consequently derived. Estimates for the case of AcS were also made, based on correlations of the data for the other An and the electronic energetics of neutral and ionic An. The nature of the bonding in the elementary molecular actinide chalcogenides (oxides and sulfides) is discussed, based on both the experimental data and the computed electronic structures. DFT calculations of ionization energies for the actinide atoms and the diatomic sulfides and oxides are relatively reliable, but the calculation of bond dissociation energies is not uniformly satisfactory, either with DFT or CCSD(T). A key conclusion from both the experimental and theoretical results is that the 5f electrons do not substantially participate in actinide-sulfur bonding. We emphasize that actinides form strikingly strong bonds with both oxygen and sulfur.

Infrared spectra and quantum chemical calculations of the uranium-carbon molecules UC, CUC, UCH, and U(CC)2.

Laser evaporation of carbon rich uranium/carbon alloy targets into condensing argon or neon matrix samples gives weak infrared absorptions that increase on annealing, which can be assigned to new uranium carbon bearing species. New bands at 827.6 cm(-1) in solid argon or 871.7 cm(-1) in neon become doublets with mixed carbon 12 and 13 isotopes and exhibit the 1.0381 carbon isotopic frequency ratio for the UC diatomic molecule. Another new band at 891.4 cm(-1) in argon gives a three-band mixed isotopic spectrum with the 1.0366 carbon isotopic frequency ratio, which is characteristic of the anti-symmetric stretching vibration of a linear CUC molecule. No evidence was found for the lower energy cyclic U(CC) isomer. Other bands at 798.6 and 544.0 cm(-1) are identified as UCH, which has a uranium-carbon triple bond similar to that in UC. Evidence is found for bicyclic U(CC)(2) and tricyclic U(CC)(3). This work shows that U and C atoms react spontaneously to form the uranium carbide U≡C and C≡U≡C molecules with uranium-carbon triple bonds.

Infrared spectra and quantum chemical calculations of the uranium carbide molecules UC and CUC with triple bonds.

Laser evaporation of carbon-rich uranium/carbon alloys followed by atom reactions in a solid argon matrix and trapping at 8 K gives weak infrared absorptions for CUO at 852 and 804 cm(-1). A new band at 827 cm(-1) becomes a doublet with mixed carbon 12 and 13 isotopes and exhibits the 1.0381 isotopic frequency ratio, which is appropriate for the UC diatomic molecule, and another new band at 891 cm(-1) gives a three-band mixed isotopic spectrum with the 1.0366 isotopic frequency ratio, which is characteristic of the linear CUC molecule. CASPT2 calculations with dynamical correlation find the C[triple bond]U[triple bond]C ground state as linear 3Sigma(u)+ with 1.840 A bond length and molecular orbital occupancies for an effective bond order of 2.83. Similar calculations with spin-orbit coupling show that the U[triple bond]C diatomic molecule has a quintet (Lambda = 5, Omega = 3) ground state, a similar 1.855 A bond length, and a fully developed triple bond of 2.82 effective bond order.

A Europium(III) Complex Embedded in a Polysulfone Host Matrix: A Flexible Film with Temperature-Responsive Ratiometric Behaviour.

An emissive europium(III) complex [C2 mim][Eu(fod)4 ] (1; C2 mim=1-ethyl-3-methyl-imidazolium; fod=1,1,1,2,2,3,3-heptafluoro-7,7-dimethyloctane-4,6-dionate) was prepared. The complex shows ratiometric thermal behaviour up to 155 °C. These unusual temperature-dependent properties arise from a solid-solid phase transition that promotes increased contact between the anion and the cation, affecting the emission profile of the emissive anion in two different ratiometric relations. A ultrabright and flexible emissive photopolymer film was obtained using polysulfone (PSU) as the host matrix of 10 % (w/w) of 1, that also induced changes on the lanthanide emissive profile with temperature. A temperature-responsive luminescent film 1/PSU is sensitivr to heating between 100 and 155 °C. Also, the emission lifetime of 1 was not affected by confinement in PSU, while its emission quantum yield was reduced from 82 to 59 %.

A Europium(III) Complex with an Unusual Anion-Cation Interaction: A Luminescent Molecular Thermometer for Ratiometric Temperature Sensing.

An unusual thermally sensitive anion-cation interaction, which is characteristic of the anion [Eu(FOD)4 ]- , occurs in the complex [CHOL][Eu(FOD)4 ] (1; CHOL=choline; FOD=1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedionate) and affects both quantum yield and thermochromic behavior. This prompted the design of an Eu3+ -based ratiometric thermometer that functions at temperatures up to 95 °C through a thermally excited state absorption of the Eu3+ ion. The reusable temperature-sensitive luminescent complex showed a range of relative sensitivity between 0.45 % C-1 at 25 °C, with an increase to 7.0 % C-1 at 95 °C. Confinement of compound 1 in a transparent film of polysulfone resulted in a higher thermal stability of 1 while its luminescence showed a strong temperature dependence.

Impact on CO2/N2 and CO2/CH4 Separation Performance Using Cu-BTC with Supported Ionic Liquids-Based Mixed Matrix Membranes.

The efficient separation of gases has industrial, economic, and environmental importance. Here, we report the improvement in gas separation performance of a polyimide-based matrix (Matrimid®5218) filled with a Cu-based metal organic framework [MOF, Cu3(BTC)2] with two different ionic liquids (ILs) confined within the pores. The chosen ILs are commonly used in gas solubilization, 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]) and 1-Ethyl-3-methylimidazolium trifluoromethanesulfonate ([EMIM][OTf]), and the incorporation of the [EMIM][BF4]@Cu-BTC and [EMIM][OTf]@Cu-BTC composites in Matrimid®5218 proved to be an efficient strategy to improve the permeability and selectivity toward CO2/N2 and CO2/CH4 mixtures.

A magnetic study of a layered lanthanide hydroxide family: Ln8(OH)20Cl4·nH2O (Ln = Tb, Ho, Er).

Three layered lanthanide hydroxides (LLHs), with the general formula Ln8(OH)20Cl4·nH2O (Ln = Tb (1), Ho (2), Er (3)), were prepared and magnetically characterized both as pure compounds and diluted within a yttrium diamagnetic matrix, LYH : xLn, LYH : 0.044Tb (1'), LYH : 0.045Ho (2'), and LYH : 0.065Er (3'). This study was complemented with theoretical calculations in order to understand the electronic configuration and the contributions to the slow relaxation behavior. In the pure compounds dominant 3D ferromagnetic interactions are observed, with a small magnetization hysteresis at 1.8 K for 1, while the magnetically diluted solid solutions display slow relaxation of magnetization at low temperatures.

A thermochromic europium(iii) room temperature ionic liquid with thermally activated anion-cation interactions.

We report the first example of an observable and reversible case of thermochromism due to the interaction of an alkylphosphonium (P6,6,6,14)+ with a ß-diketonate (1,1,1,2,2,3,3-heptafluoro-7,7-dimethyloctane-4,6-dionate-fod) of an europium(iii) tetrakis-ß-diketonate room temperature ionic liquid. This thermochromism is characterized by the conversion of a light yellow viscous liquid, at room temperature, to a reddish substance close to 80 °C. The reversibility of this optical effect was highlighted by the thermal stability of the Eu(iii) complex.

Metal-organic frameworks based on uranyl and phosphonate ligands.

Three new crystalline metal-organic frameworks have been prepared from the reaction of uranyl nitrate with nitrilotris(methylphosphonic acid) [H6nmp, N(CH2PO3H2)3], 1,4-phenylenebis(methylene)diphosphonic acid [H4pmd, C6H4(PO3H2)2], and (benzene-1,3,5-triyltris(methylene))triphosphonic acid [H6bmt, C6H3(PO3H2)3]. Compound [(UO2)2F(H3nmp)(H2O)]·4H2O (I) crystallizes in space group C2/c, showing two crystallographically independent uranyl centres with pentagonal bipyramidal coordination geometries. While one metal centre is composed of a {(UO2)O3(µ-F)}2 dimer, the other comprises an isolated {(UO2)O5} polyhedron. Compound [(UO2)(H2pmd)] (II) crystallizes in space group P21/c, showing a centrosymmetric uranyl centre with an octahedral {(UO2)O4} coordination geometry. Compound [(UO2)3(H3bmt)2(H2O)2]·14H2O (III) crystallizes in space group P\bar 1, showing two crystallographically independent uranyl centres. One uranyl centre is a {(UO2)O5} pentagonal bipyramid similar to that in (I), while the other is a {(UO2)O4} centrosymmetric octahedron similar to that in (II). Compounds (I) and (III) contain solvent-accessible volumes accounting for ca 23.6 and 26.9% of their unit-cell volume, respectively. In (I) the cavity has a columnar shape and is occupied by disordered water molecules, while in (III) the cavity is a two-dimensional layer with more ordered water molecules. All compounds have been studied in the solid state using FT-IR spectroscopy. Topological studies show that compounds (I) and (III) are trinodal, with 3,6,6- and 4,4,6-connected networks, respectively. Compound (II) is instead a 4-connected uninodal network of the type cds.

Indenyl ring slippage in crown thioether complexes [IndMo(CO)2L]+ and C-S activation of trithiacyclononane: experimental and theoretical studies.

The macrocycle 1,4,7-trithiacyclononane (ttcn) reacts with [(η(5)-Ind)Mo(CO)(2)(NCMe)(2)](+) (or [(η(5)-Ind)Mo(CO)(2)(κ(2)-dme)](+)) to give [(η(3)-Ind)Mo(CO)(2)(κ(3)-ttcn)](+) as the BF(4)(-) salt (1), but its reaction with [(η(5)-Ind)Mo(CO)(2)(C(3)H(6))(FBF(3))] affords the C-S bond cleavage product [(η(5)-Ind)Mo(CO)(κ(3)-1,4,7-trithiaheptanate)]BF(4) (6), which has been characterised by X-ray crystallography (Ind = C(9)H(7), indenyl). In contrast to ttcn, the macrocycles 1,3,5-trithiane (tt) and 1,4,7,10-tetrathiacyclododecane (ttcd) fail to induce changes in the coordination mode of indenyl: tt and ttcd react with [(η(5)-Ind)Mo(CO)(2)(NCMe)(2)](+) (or [(η(5)-Ind)Mo(CO)(2)(κ(2)-dme)](+)) to give [(η(5)-Ind)Mo(CO)(2)(κ(2)-tt)](+) (2), characterised by X-ray crystallography, and [(η(5)-Ind)Mo(CO)(2)(κ(2)-ttcd)](+) (3), respectively. The cyclopentadienyl (Cp = C(5)H(5)) analogues [(η(5)-CpMo(CO)(2)(κ(2)-tt)](+) (4) and [(η(5)-CpMo(CO)(2)(κ(2)-ttcn)](+) (5) have also been synthesised and 5 characterised by X-ray crystallography. DFT calculations showed that the η(5)-Ind/Cp coordination mode is always the most stable. However, a molecular dynamics study of the macrocycles conformations revealed that the major conformer of ttcn was a chair, which favoured κ(3) coordination. As indenyl complexes undergo slippage with a small barrier (<10 kcal mol(-1)), the kinetically preferred species [(η(3)-Ind)Mo(CO)(2)(κ(3)-ttcn)](+) (1) is the observed one. The conversion to 6 proceeds stepwise, with loss of ethylene followed by loss of CO, as calculated by DFT, with a barrier of 38.7 kcal mol(-1), consistent with the slow uncatalysed reaction.

A highly efficient dioxo(mu-oxo)molybdenum(VI) dimer catalyst for olefin epoxidation.

The oxo-bridged dimer [Mo(2)O(4)(mu(2)-O)Cl(2)(pzH)(4)] (1; pzH = pyrazole) exhibits unusually high activity in the liquid-phase catalytic epoxidation of the cyclic olefins cyclooctene and (R)-(+)-limonene under mild conditions and in the absence of additional organic solvents, using tert-butyl hydroperoxide as the oxidant. The complex is stable under the reaction conditions and can be used in further catalytic runs without significant loss of performance. An X-ray crystallographic investigation reveals that 1 has an unprecedented and extremely rare all-cis configuration at each of the MoO(2)-(mu(2)-O)Cl(pzH)(2) cores, which can be understood by considering supramolecular contacts and geometric factors.